CN103880779A - Method utilizing quaternary ammonium heteropolyate to catalyze alkene epoxidation - Google Patents
Method utilizing quaternary ammonium heteropolyate to catalyze alkene epoxidation Download PDFInfo
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- CN103880779A CN103880779A CN201210559384.1A CN201210559384A CN103880779A CN 103880779 A CN103880779 A CN 103880779A CN 201210559384 A CN201210559384 A CN 201210559384A CN 103880779 A CN103880779 A CN 103880779A
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- quaternary ammonium
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- alkene
- ammonium salt
- auxiliary agent
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention provides a method utilizing quaternary ammonium heteropolyate to catalyze alkene epoxidation. Alkene and an oxidant carry out reactions in the presence of a quaternary ammonium heteropolyate catalyst, a reductive auxiliary agent, and an organic solvent for 2 to 10 hours at a temperature of 50 to 80 DEG C. After the reaction, the precipitated catalyst can be separated and recycled, and the reaction liquid is subjected to a steaming treatment so as to obtain the target epoxides. The method has the advantages of simple technology, mild conditions, green, and environment-friendliness, and has a vast industrial application prospect, and moreover, the catalyst is easy to separate, recycle and reutilize.
Description
Technical field
The invention belongs to chemical catalysis field, a kind of method of heteropolyacid quaternary ammonium salt catalyzing expoxidation of olefines is particularly provided.
Background technology
Alkene epoxidation is one of most important reaction in chemical industry, and its epoxidation product is the raw material of the multiple important Chemicals of preparation, is widely used in the various fields such as organic synthesis, fine chemistry industry and petrochemical complex.The method that tradition is prepared epoxy compounds is chlorohydrination and conjugated oxidation, and they all exist more serious problem of environmental pollution.People are devoted to develop that flow process is simple, by product is few and free of contamination olefin epoxidation process always for many years, at present report take green oxygen source hydrogen peroxide in the olefin epoxidation catalysts of oxygen source, having reaction, to control the heteropolyacid quaternary ammonium salt of phase transition characteristic be that a class is compared with the catalyzer of tool industrial prospect.This type of bibliographical information has:
Document: Xi Z W, Zhou N, SunY, Li K L.Reaction-ControlledPhase-Transfer Catalysis for Propylene Epoxidation to PropyleneOxide[J] .Science, 2001,292:1139
Document: Gao S, Li M, LvY, Zhou N, Xi Z W. Epoxidation ofPropylene with Aqueous Hydrogen Peroxide on a Reaction-ControlledPhase-Transfer Catalyst[J] .Organic Process Research & Development, 2004,8:131
Document: Li J, Xi Z W, Gao S, An environmentally benign route forepichlorohydrin from allyl chloride epoxidation catalyzed byheteropolyphosphatotungstate[J] .Research on Chemical Intermediates, 2007,33:523
Document: CN101045716B, CN101205219B and CN100532371C etc.
In above-mentioned bibliographical information, alkene needs excessive more, to guarantee the completely consumed of H2O2, catalyzer can efficiently be separated out and cycling and reutilization, but this has limited the application of this catalyst system.The present invention is by adding the mode of reductibility auxiliary agent, H2O2 can be consumed completely, has reduced the charging capacity of olefin substrate, successfully catalysis the epoxidation of a series of alkene, this technique has higher olefin conversion, selectivity and cyclical stability, and application prospect is huge.
Summary of the invention
Alkene, oxygenant react under heteropolyacid quaternary ammonium salt catalyst, reductibility auxiliary agent and organic solvent exist, 50 ~ 80 ℃ of temperature of reaction, reaction times 2 ~ 10h, reaction is separated out catalyzer after finishing and can be separated and re-use, and reaction solution obtains target epoxide by distillation.
Heteropolyacid quaternary ammonium salt catalyst molecular composition Q
mh
npM
xo
yq is quaternary ammonium salt cationic, quaternary ammonium salt is at least one in 4-butyl ammonium, dodecyl trismethylamine salt, cetyl trimethyl amine salt, Octadecyl trimethylamine salt or two octadecyl dimethyl amine salt, metal M is W and/or Mo, 1≤m≤7,1≤x≤12,0≤n≤4,10≤y≤40.
Oxygenant can be aqueous hydrogen peroxide solution or be dissolved in the hydrogen peroxide in organic solvent.Wherein the hydrogen peroxide in organic solvent can obtain by steaming water pretreatment, and it steams water pretreatment process and condition is: in the there-necked flask of 250ml, add a certain amount of organic solvent and aqueous hydrogen peroxide solution.Condensation reflux device and water trap are installed on flask, start at normal temperatures and pressures to stir, slowly rising temperature to 30 ~ 50 ℃, pressure drops to 0.005 ~ 0.01MPa, the system steaming water that comes to life, water layer to water trap no longer raises, and stops heating decompression, obtains the H2O2-oxidation in organic solvent agent of colourless homogeneous.
Organic solvent is at least one in chloroform, ethylene dichloride, tetracol phenixin, benzene,toluene,xylene, heavy aromatics, acetonitrile, butylacetate, dimethyl formamide, tributyl phosphate, tetrabutyl urea, chlorallylene or ethyl acetate.
Reductibility auxiliary agent is at least one of Sulfothiorine, xitix, alkene, Sodium Nitrite, S-WAT, nitrogen protoxide or sodium borohydride.Alkene in reductibility auxiliary agent is at least one of propylene, chlorallylene, 1-butylene, 2-butylene.Reductibility auxiliary agent can add before reaction together with reactant, also can in reaction process, add.
In reaction solution, the content of oxidants hydrogen peroxide is 30 ~ 100 grams per liter reaction solutions, the content of quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer is 2 ~ 60 grams per liter reaction solutions, the content of reductibility auxiliary agent is 1 ~ 250 grams per liter reaction solution, the content of substrate alkene is 30 ~ 150 grams per liter reaction solutions, the content of water is 1 ~ 200 grams per liter reaction solution, and all the other are organic solvent.
Substrate alkene is the chain of C3 ~ C15 or the alkene of ring-type, can be monoolefine, or has the polyene hydrocarbon of more than 2 ethylene linkage.
Embodiment
Give further instruction below by embodiment to the present invention:
Embodiment 1: the styrene catalyzed epoxidation of heteropolyacid quaternary ammonium salt
(1) prepare heteropolyacid quaternary ammonium salt catalyst: reference Journal ofMolecularCatalysis A, 2001,166:219..
Weighing 2.50g wolframic acid, to join 10ml mass concentration be 30% H
2o
2in, be heated to while stirring 60 ℃, after 60 minutes, obtain colourless transparent solution.Be 85% phosphoric acid to adding 0.29g mass concentration in this dissolving, add 20ml distilled water and continue to stir 30min.Weigh 2.5g palmityl trimethyl ammonium chloride and be dissolved in the ethylene dichloride of 40ml, this solution is added drop-wise in above-mentioned hydrogen peroxide solution fast, continue to stir 60min, be precipitated.The PH that is precipitated to filtrate with distilled water wash approximates 4.Filtrate vacuum-drying at 50 ~ 60 ℃, obtains phosphorus heteropoly tungstic acid quaternary amine catalyzer.
(2) cinnamic epoxidation reaction: in 100ml glass reaction bottle, add heteropolyacid quaternary ammonium salt catalyst 0.3g obtained above, ethylene dichloride 30ml, vinylbenzene 3.3g, the H that concentration is 50%
2o
22.1g stirs after 5h at 60 ℃ of temperature of reaction, adds 0.5g xitix, then continues reaction 0.5h, cooling and solid catalyst, and catalyst recovery yield is 97%.Reaction solution is by gas chromatographic analysis, and Styryl oxide is to H
2o
2productive rate be 90%.
Embodiment 2: heteropolyacid quaternary ammonium salt catalysis epoxidation of cyclohexene
(1) prepare heteropolyacid quaternary ammonium salt catalyst: with embodiment 1
(2) epoxidation reaction of tetrahydrobenzene: in 100ml glass reaction bottle, add heteropolyacid quaternary ammonium salt catalyst 0.6g, ethylene dichloride 30ml, tetrahydrobenzene 5.6g, the H that concentration is 50%
2o
24.2g stirs after 4h at 50 ℃ of temperature of reaction, adds 0.5g S-WAT, then continues reaction 0.5h, cooling and solid catalyst, and catalyst recovery yield is 98%.Reaction solution is by gas chromatographic analysis, and epoxy cyclohexane is to H
2o
2productive rate be 92%.
Embodiment 3: heteropolyacid quaternary ammonium salt catalysis cyclopentenes epoxidation
(1) prepare heteropolyacid quaternary ammonium salt catalyst: with embodiment 1
(2) epoxidation reaction of cyclopentenes: in 100ml glass reaction bottle, add heteropolyacid quaternary ammonium salt catalyst 0.6g, ethylene dichloride 40ml, vinylbenzene 4.5g, the H that concentration is 50%
2o
24.2g stirs after 2h at 50 ℃ of temperature of reaction, adds 0.5g Sulfothiorine, then continues reaction 0.5h, cooling and solid catalyst, and catalyst recovery yield is 95%.Reaction solution is by gas chromatographic analysis, and cyclopentane epoxide is to H
2o
2productive rate be 93%.
Embodiment 4: heteropolyacid quaternary ammonium salt catalysis α-pinene epoxidation
(1) prepare heteropolyacid quaternary ammonium salt catalyst: with embodiment 1
(2) epoxidation reaction of α-pinene: in 100ml glass reaction bottle, add heteropolyacid quaternary ammonium salt catalyst 0.3g, H
2o
2concentration is toluene-tributyl phosphate reaction solution 50ml of 1.0mmol/g, α-pinene 6.0g, and chlorallylene 11.0g, 0.1g pyridine stirs after 6h cooling and solid catalyst at 50 ℃ of temperature of reaction.Reclaim catalyzer and carry out circulation experiment.
Technique of the present invention is simple, and mild condition, catalyzer are easy to separation and recovery, environmental protection, have very large prospects for commercial application.
Claims (10)
1. the method for a heteropolyacid quaternary ammonium salt catalyzing expoxidation of olefines, it is characterized in that: alkene, oxygenant react under heteropolyacid quaternary ammonium salt catalyst, reductibility auxiliary agent and organic solvent exist, 50 ~ 80 ℃ of temperature of reaction, reaction times 2 ~ 10h, reaction is separated out catalyzer after finishing and can be separated and re-use, and reaction solution obtains target epoxide by distillation.
2. according to the method for claim 1, it is characterized in that: heteropolyacid quaternary ammonium salt catalyst molecular composition Q
mh
npM
xo
y, Q is quaternary ammonium salt cationic, quaternary ammonium salt be in 4-butyl ammonium, dodecyl trismethylamine salt, cetyl trimethyl amine salt, Octadecyl trimethylamine salt or two octadecyl dimethyl amine salt at least one or more than two kinds; Metal M is W and/or Mo, 1≤m≤7,1≤x≤12,0≤n≤4,10≤y≤40.
3. according to the method for claim 1, it is characterized in that: oxygenant can be aqueous hydrogen peroxide solution or be dissolved in the hydrogen peroxide in organic solvent.
4. according to the method for claim 1, it is characterized in that: reductibility auxiliary agent is at least one of Sulfothiorine, xitix, alkene, Sodium Nitrite, S-WAT, nitrogen protoxide or sodium borohydride or more than two kinds; Alkene in reductibility auxiliary agent is at least one of propylene, chlorallylene, 1-butylene, 2-butylene or more than two kinds.
5. according to the method for claim 1 or 3, it is characterized in that: reductibility auxiliary agent can add before reaction together with reactant, also can in reaction process, add;
Organic solvent be in chloroform, ethylene dichloride, tetracol phenixin, benzene,toluene,xylene, heavy aromatics, acetonitrile, butylacetate, dimethyl formamide, tributyl phosphate, tetrabutyl urea, chlorallylene or ethyl acetate at least one or more than two kinds.
6. according to the method for claim 1 or 2, it is characterized in that: the content of quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer is 2 ~ 60 grams per liter reaction solutions.
7. according to the method for claim 1 or 3, it is characterized in that: the content of oxidants hydrogen peroxide is 30 ~ 100 grams per liter reaction solutions.
8. according to the method for claim 1 or 4, it is characterized in that: the content of reductibility auxiliary agent is 1 ~ 250 grams per liter reaction solution.
9. according to the method for claim 1, it is characterized in that: the content of substrate alkene is 30 ~ 150 grams per liter reaction solutions; Substrate alkene is the chain of C3 ~ C15 or the alkene of ring-type.
10. according to the method for claim 1, it is characterized in that: the content of water is 1 ~ 200 grams per liter reaction solution.
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Cited By (7)
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|---|---|---|---|---|
| CN104098531A (en) * | 2014-07-25 | 2014-10-15 | 南京红太阳新材料有限公司 | Synthetic method for 1,2-epoxybutane |
| CN105618138A (en) * | 2014-10-29 | 2016-06-01 | 中国科学院大连化学物理研究所 | Immobilized tungstophosphoric heteropoly acid catalyst and use thereof |
| CN109046452A (en) * | 2018-05-29 | 2018-12-21 | 南京大学 | A kind of supported heteropolyacid catalyst and its preparation method and application |
| CN109603890A (en) * | 2019-01-23 | 2019-04-12 | 中国天辰工程有限公司 | A kind of regeneration method of polyoxometallate |
| CN110833866A (en) * | 2019-11-14 | 2020-02-25 | 江苏扬农化工集团有限公司 | Method for improving recovery rate of epoxidation catalyst |
| CN111036293A (en) * | 2020-01-02 | 2020-04-21 | 江苏扬农化工集团有限公司 | Preparation method of heteropoly acid catalyst |
| CN111253342A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Method for catalyzing olefin epoxidation by heteropoly acid quaternary ammonium salt |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104098531A (en) * | 2014-07-25 | 2014-10-15 | 南京红太阳新材料有限公司 | Synthetic method for 1,2-epoxybutane |
| CN105618138A (en) * | 2014-10-29 | 2016-06-01 | 中国科学院大连化学物理研究所 | Immobilized tungstophosphoric heteropoly acid catalyst and use thereof |
| CN105618138B (en) * | 2014-10-29 | 2018-01-09 | 中国科学院大连化学物理研究所 | Solid-carrying type phosphorus heteropoly tungstic acid catalyzer and its application |
| CN109046452A (en) * | 2018-05-29 | 2018-12-21 | 南京大学 | A kind of supported heteropolyacid catalyst and its preparation method and application |
| CN109046452B (en) * | 2018-05-29 | 2022-02-08 | 南京大学 | Immobilized heteropolyacid catalyst and preparation method and application thereof |
| CN111253342A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Method for catalyzing olefin epoxidation by heteropoly acid quaternary ammonium salt |
| CN109603890A (en) * | 2019-01-23 | 2019-04-12 | 中国天辰工程有限公司 | A kind of regeneration method of polyoxometallate |
| CN110833866A (en) * | 2019-11-14 | 2020-02-25 | 江苏扬农化工集团有限公司 | Method for improving recovery rate of epoxidation catalyst |
| CN111036293A (en) * | 2020-01-02 | 2020-04-21 | 江苏扬农化工集团有限公司 | Preparation method of heteropoly acid catalyst |
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